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pH measurements
The probe, from chemistry to voltage
to a number
Monroe L. Weber-Shirk
pH probe
Buffered KCl solution
4 M KCl solution
Reference electrode
Silver/silver chloride electrode
Sensing electrode
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Reference Voltage +
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Call it+ zero!
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pH 4 solution (high H+)
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pH Measurements
The porous frit provides electrical contact between
the solution and the electrolyte
Must be in contact with the sample solution
Probe wont work well if frit is clogged (fouled)
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Difficult Measurements?
pH is difficult to measure in poorly buffered
solutions
Distilled water
Rain
Between pKs of dilute buffers
E E0
RT FH
lnG
nF G
HH
I
JJ
K
RT ln(10) FH
logG
G
nF
HH
I
JJ
K
RT ln(10)
0
E =E +
pH
- pH
nF
E E ) nF
(
pH pH 0
RT ln(10)
Faraday constant
Gas constant
E0
H
Voltage at
J
R 8.314
mol K
Coulombs
F 96500
mol e
n 1 mol e
Nernst Equation
pH pH 0
0
E
E
(
) nF
RT ln(10)
E
E nF
0
pH = pH + 0 -
T
T R ln(10)
J
R 8.314
mol K
Coulombs
F 96500
mol e
n 1 mol e
pH Calibration
It would be possible to make a pH measurement
without any calibration
Based on theoretical values
This is how the software recognizes buffers!
The Challenge
0 to 3 known buffers used as standards
Temperature compensation optional
E
Buffer pH
pH
Calibration Cases
0 or 1 standards w/ Temperature
nF E 0 E
0
pH
pH
R ln(10) T 0 T
ideal
pH =k pH
E
E
0
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pH
T 0 T
pH k ideal
pH
E
7
T
E
E
ideal
pH =k pH 1 - +pH 1
T T
ideal
k pH
ideal
k pH
nF
R ln(10)
K
5040.8
Volt
E (mV)
T (C)
Buffer
pH
23
185
24
-170
20
10
pH